WO2012147767A1 - Procédé de production de matériau actif d'électrode positive pour batterie secondaire au lithium - Google Patents

Procédé de production de matériau actif d'électrode positive pour batterie secondaire au lithium Download PDF

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Publication number
WO2012147767A1
WO2012147767A1 PCT/JP2012/061036 JP2012061036W WO2012147767A1 WO 2012147767 A1 WO2012147767 A1 WO 2012147767A1 JP 2012061036 W JP2012061036 W JP 2012061036W WO 2012147767 A1 WO2012147767 A1 WO 2012147767A1
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Prior art keywords
positive electrode
active material
electrode active
lithium
secondary battery
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PCT/JP2012/061036
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English (en)
Japanese (ja)
Inventor
功 河邊
彰彦 白川
学 織地
明央 利根川
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昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to US14/113,731 priority Critical patent/US9745194B2/en
Priority to CN201280020124.5A priority patent/CN103503207B/zh
Priority to JP2013512393A priority patent/JP6055761B2/ja
Publication of WO2012147767A1 publication Critical patent/WO2012147767A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a positive electrode active material for a lithium secondary battery.
  • LiMPO 4 (M is a transition metal), which is an olivine-type lithium metal phosphate, has a relatively large electric capacity and is less expensive than LiCoO 2 that has been widely used as a positive electrode active material for lithium secondary batteries. Since a battery can be made, it is expected as a positive electrode active material for a lithium secondary battery, particularly a large-sized lithium secondary battery for automobiles (see Patent Documents 1 and 2).
  • LiMPO 4 Solid phase method as the synthesis of LiMPO 4, hydrothermal method, coprecipitation, etc.
  • Various synthetic methods have been proposed, for removing impurities contained in LiMPO 4 obtained raise the purity, typically, After the synthesis, the lithium metal phosphate (LiMPO 4 ) is washed (see Patent Documents 3 and 4).
  • Patent Documents 3 and 4 disclose that the positive electrode active material for a lithium secondary battery containing lithium metal phosphate is washed with a pH buffer solution to remove impurities and increase the purity.
  • the lithium metal phosphate is LiFePO 4
  • impurities including divalent iron such as FeSO 4 , FeO, and Fe 3 (PO 4 ) 2 without dissolving Fe of LiFePO 4.
  • impurities such as Li 3 PO 4 and Li 2 CO 3 contained in LiFePO 4 can be reduced.
  • Patent Documents 3 and 4 disclose a cleaning liquid that suppresses dissolution of Fe in lithium iron phosphate LiFePO 4 , but particularly discloses a cleaning liquid that suppresses dissolution of Li in LiFePO 4. ⁇ No suggestion.
  • the results in Table 1 are for lithium iron phosphate LiFePO 4 .
  • the discharge capacity shown in Table 1 is a charge / discharge cycle in which a constant current and a constant voltage are charged to 3.9 V at a temperature of 25 ° C. and a current of 0.1 C, and then a constant current is discharged to 2.3 V at a current of 0.1 C.
  • the measurement results of the second discharge capacity are shown repeatedly. From Table 1, it can be seen that the discharge capacity increases when the water washing time is extended to 1 minute and 2 minutes, but the discharge capacity decreases after 3 minutes.
  • the reason why the discharge capacity decreases as the cleaning time becomes longer is that when the water cleaning time is extended, the color of the lithium iron phosphate LiFePO 4 powder changes from light green to blue. It is presumed that lithium ions are eluted from the surface of No. 4 and a heterogeneous layer is formed on the surface, and this heterogeneous layer inhibits the diffusion of lithium ions.
  • the present invention has been made in view of the above problems, and the elution of lithium ions from the lithium metal phosphate is suppressed during washing after synthesizing the olivine type lithium metal phosphate, and the charge / discharge capacity and discharge are reduced. It is an object of the present invention to provide a method for producing a positive electrode active material for a lithium secondary battery comprising an olivine type lithium metal phosphate, which can constitute a lithium secondary battery having an improved rate.
  • the present invention provides the following means.
  • a lithium metal phosphate represented by the composition formula LiMPO 4 the element M is one or two or more transition metals of Fe, Mn, Co, or Ni
  • the lithium metal phosphorus The manufacturing method of the positive electrode active material for lithium secondary batteries which wash
  • the solute of the cleaning liquid contains at least one of LiClO 4 , Li 2 CO 3 , LiOH, LiPF 6 , Li 3 PO 4 , LiH 2 PO 4 , and CH 3 CO 2 Li. Manufacturing method of positive electrode active material for lithium secondary battery.
  • [3] The method for producing a positive electrode active material for a lithium secondary battery according to any one of [1] or [2], wherein the solvent of the cleaning liquid is a liquid containing water.
  • [4] The method for producing a positive electrode active material for a lithium secondary battery according to [3], wherein the liquid containing water is water.
  • [5] The method for producing a positive electrode active material for a lithium secondary battery according to any one of [1] to [4], wherein the cleaning liquid containing lithium ions has a pH of 5 or more and 9 or less.
  • [6] The method for producing a positive electrode active material for a lithium secondary battery according to any one of [1] to [5], wherein the cleaning is performed with a temperature of the cleaning liquid containing lithium ions being 15 ° C.
  • [13] The method for producing a positive electrode active material for a lithium secondary battery according to [13], wherein heating is performed at a temperature of 1 hour to 20 hours.
  • [15] The lithium secondary battery according to any one of [1] to [11], wherein after the cleaning, a layer containing carbon is formed on at least a part of a surface of the lithium metal phosphate.
  • [16] The method for producing a positive electrode active material for a lithium secondary battery according to any one of [1] to [15], wherein the transition metal (M) in the LiMPO 4 is either Fe or Mn. .
  • a lithium secondary battery in which elution of lithium ions from the lithium metal phosphate is suppressed during washing after synthesizing the olivine-type lithium metal phosphate and charge / discharge capacity and discharge rate are improved.
  • the manufacturing method of the positive electrode active material for lithium secondary batteries which consists of olivine type lithium metal phosphate which can comprise can be provided.
  • a method for producing a positive electrode active material for a lithium secondary battery includes synthesizing a lithium metal phosphate represented by the composition formula LiMPO 4 and then washing the lithium metal phosphate with lithium ions. It is characterized by washing with.
  • the element M of LiMPO 4 is one or two or more transition metals of Fe, Mn, Co, or Ni.
  • the method for synthesizing the lithium metal phosphate is not particularly limited, and a hydrothermal synthesis method, a solid phase synthesis method, or the like can be used.
  • the solute of the cleaning solution containing lithium ions is not particularly limited as long as it dissolves to generate lithium ions, but LiClO 4 , Li 2 CO 3 , LiOH, LiPF 6 , Li 3 PO 4 , LiH 2 PO 4 , CH 3 CO preferably contains at least one 2 Li. What does not produce lithium ion may be contained as a solute of the cleaning liquid containing lithium ion.
  • the lithium ion concentration of the cleaning liquid containing lithium ions is preferably 0.01 mol / L or more, and more preferably 1 mol / L or more. If it is less than 0.01 mol / L, the suppression effect of lithium ion elution from the lithium metal phosphate LiMPO 4 is too small, and it may be difficult to increase the charge / discharge capacity and the discharge rate, This is because if it is 1 mol / L or more, the lithium ion elution suppression effect is large, and the charge / discharge capacity and discharge rate can be sufficiently increased.
  • the solvent of the cleaning liquid is preferably a liquid containing water, and more preferably water.
  • the purpose of washing with a washing solution containing lithium ions is to dissolve and remove the synthetic raw material contained in the synthesized lithium metal phosphate as ions.
  • lithium metal phosphate LiFePO 4 is synthesized using FeSO 4 as a transition metal (M) source
  • the raw materials contained in lithium metal phosphate LiFePO 4 are dissolved as sulfate ions after synthesis. It is for removing.
  • the pH of the cleaning liquid containing lithium ions is preferably 5 or more and 9 or less. This is because when the pH is 5 or less or 9 or more, the metal M is easily dissolved from LiMPO 4 .
  • the pH can be adjusted by adding sulfuric acid or aqueous ammonia to the cleaning liquid. The pH can be measured with a pH meter based on the glass electrode method.
  • Cleaning with a cleaning solution containing lithium ions is preferably performed at a temperature of 15 ° C. or higher. This is because if it is lower than 15 ° C., the efficiency of removing impurities mixed in LiMPO 4 may be lowered.
  • the washing time is preferably within 1 hour. This is because if it is longer than 1 hour, LiMPO 4 may be oxidized by oxygen dissolved in the cleaning liquid.
  • the cleaning preferably includes a step of stirring a cleaning liquid containing lithium ions. This is because, by stirring, impurities mixed with LiMPO 4 are well dissolved in the cleaning liquid, and impurities can be prevented from remaining.
  • any one or two of Nb and V is contained in the lithium metal phosphate after synthesis. This is because when charging / discharging including Nb or V is repeated, a decrease in capacity is suppressed.
  • a lithium metal phosphate containing Nb or V can be produced by adding a substance containing Nb or V to the lithium metal phosphate synthesis raw material. Examples of the substance containing Nb include niobium phenoxide (Nb (OC 6 H 5 ) 5 , niobium chloride NbCl 5 , and the substance containing V, for example, ammonium vanadate (NH 4 VO 3 ).
  • the particle size of the lithium metal phosphate after synthesis is preferably 20 to 200 nm. This is because if it is smaller than 20 nm, the crystallinity is lowered and the capacity may be lowered, and if it is larger than 200 nm, the charge / discharge speed is lowered.
  • the pH of the solution after synthesis the particle size of the lithium metal phosphate can be adjusted to 20 to 200 nm.
  • the pH of each of the lithium (Li) source, transition metal (M) source, phosphoric acid (PO 4 ) source concentration, transition metal (M) source type, synthesis temperature, synthesis time, and stirring intensity should be adjusted. The range changes.
  • As a method for adjusting the pH for example, addition of sulfuric acid or ammonia water to the raw material can be mentioned.
  • the ratio of the number of Li atoms to the number of M atoms in the region from the surface of the synthesized lithium metal phosphate to a depth of 2 nm is preferably 0.7 or more and less than 1.1.
  • the ratio of the number of Li atoms to the number of M atoms can be measured, for example, by TEM-EELS (Electron Energy Loss Spectroscopy). In the lithium metal phosphate synthesized by a usual method, the ratio of the number of Li atoms to the number of M atoms is close to 1.
  • the lithium metal phosphate After washing, it is preferable to mix the lithium metal phosphate and the liquid in which the substance containing carbon atoms is dissolved. This is because a layer containing carbon can be formed on at least a part of the surface of the lithium metal phosphate, and the conductivity can be improved.
  • the liquid that dissolves the substance containing carbon atoms is not particularly limited as long as it is a liquid having low reactivity with LiMPO 4. For example, water, ethanol, and acetone can be used. More preferably, after the mixing, the solvent of the liquid in which the substance containing carbon atoms is dissolved is removed. This is because a layer containing carbon with few impurities can be formed on at least a part of the surface of the lithium metal phosphate, and the conductivity can be further improved.
  • the mixture of the lithium metal phosphate and the substance containing carbon atoms is reduced to 1 at a temperature of 400 ° C. to 900 ° C. in an atmosphere having an oxygen concentration of 1% or less. It is more preferable to heat for not less than 20 hours. This is because LiMPO 4 is oxidized when the oxygen concentration is higher than 1%.
  • the temperature is lower than 400 ° C., the carbon atom content of the layer containing carbon formed on the surface of the lithium metal phosphate is lowered, and the conductivity is lowered.
  • LiMPO 4 This is because crystal grains grow and the charge / discharge rate decreases.
  • the time is shorter than 1 hour, the carbon atom content of the layer containing carbon formed on the surface of the lithium metal phosphate is lowered and the conductivity is lowered. If the time is longer than 20 hours, the energy for heating the furnace is reduced. Because it is useless.
  • a carbon-containing layer on at least a part of the surface of the lithium metal phosphate. This is because the conductivity can be improved.
  • the transition metal (M) constituting the lithium metal phosphate LiMPO 4 can be any one or more of Fe, Mn, Co, or Ni, and in particular, is either Fe or Mn. It is preferable. That is, as the lithium metal phosphate, either LiFePO 4 or LiMnPO 4 , or LiFeM′PO 4 (M ′ is another transition metal that is not Fe) or LiMnM′PO 4 (M ′ is other than Mn) It is preferable that any one of transition metals). Moreover, as the transition metal constituting the lithium metal phosphate LiMPO 4 (M), it is also preferred to include both Fe and Mn.
  • the lithium metal phosphate is preferably LiFeMnPO 4 or LiFeMnM′PO 4 (M ′ is another transition metal that is neither Fe nor Mn). Since both LiFePO 4 and LiMnPO 4 have a high theoretical capacity (LiFePO 4 is 170 mAh / g, LiMnPO 4 is 171 mAh / g), either LiFePO 4 or LiMnPO 4 or LiFeM′PO 4 (M ′ is Fe) Not any other transition metal) or LiMnM′PO 4 (M ′ is another transition metal that is not Mn), or LiFeMnPO 4 or LiFeMnM′PO 4 (M ′ is neither Fe nor Mn) Battery capacity per unit mass can be increased.
  • the synthesis of the lithium metal phosphate LiMPO 4 before washing is preferably performed by hydrothermal synthesis. This is because the hydrothermal synthesis method can obtain LiMPO 4 having a small particle size at a relatively low temperature in a short time.
  • the hydrothermal synthesis of the lithium metal phosphate LiMPO 4 before washing includes a liquid containing water, a lithium (Li) source, one or more transition metal (M) sources, and a phosphoric acid (PO 4 ) source. Can be used as raw materials.
  • the hydrothermal synthesis of the lithium metal phosphate LiMPO 4 before washing can be performed using a liquid containing water, Li 3 PO 4 , and one or more transition metal (M) sources as raw materials. .
  • a transition metal (M) source containing either FeSO 4 or MnSO 4 can be used. Accordingly, LiFePO 4 or LiMnPO 4 as a lithium metal phosphate, or LiFeM′PO 4 (M ′ is another transition metal that is not Fe) or LiMnM′PO 4 (M ′ is another transition metal that is not Mn). Can be synthesized.
  • a transition metal (M) source containing both FeSO 4 and MnSO 4 can be used.
  • LiFeMnPO 4, or, LiFeMnM'PO 4 (M 'is other transition metals neither Fe and Mn) can be synthesized as a lithium metal phosphate.
  • LiOH can be used as a lithium (Li) source.
  • H 3 PO 4 can be used as a phosphoric acid (PO 4 ) source.
  • a lithium secondary battery according to an embodiment of the present invention includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode active material contained in the positive electrode is manufactured by the above method. By providing such a positive electrode active material, the capacity and discharge rate of the lithium secondary battery can be improved.
  • the positive electrode, the negative electrode, and the nonaqueous electrolyte constituting the lithium secondary battery will be described in order.
  • a positive electrode a sheet comprising a positive electrode mixture containing a positive electrode active material, a conductive additive and a binder, and a positive electrode current collector bonded to the positive electrode mixture Shaped electrodes can be used. Further, as the positive electrode, a pellet type or sheet-shaped positive electrode formed by forming the above positive electrode mixture into a disk shape can also be used.
  • the lithium metal phosphate produced by the above method is used.
  • a conventionally known positive electrode active material may be mixed with the lithium metal phosphate.
  • Binders include polyethylene, polypropylene, ethylene propylene copolymer, ethylene propylene terpolymer, butadiene rubber, styrene butadiene rubber, butyl rubber, polytetrafluoroethylene, poly (meth) acrylate, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, poly Examples include epichlorohydrin, polyphasphazene, polyacrylonitrile, and the like.
  • examples of the conductive aid include conductive metal powders such as silver powder; conductive carbon powders such as furnace black, ketjen black, and acetylene black; carbon nanotubes, carbon nanofibers, and vapor grown carbon fibers.
  • conductive metal powders such as silver powder
  • conductive carbon powders such as furnace black, ketjen black, and acetylene black
  • carbon nanotubes, carbon nanofibers, and vapor grown carbon fibers examples of the conductive aid.
  • vapor grown carbon fiber is preferable.
  • the vapor grown carbon fiber preferably has a fiber diameter of 5 nm to 0.2 ⁇ m.
  • the ratio of fiber length / fiber diameter is preferably 5 to 1000.
  • the content of vapor grown carbon fiber is preferably 0.1 to 10% by mass with respect to the dry mass of the positive electrode mixture.
  • examples of the positive electrode current collector include a conductive metal foil, a conductive metal mesh, and a conductive metal punching metal.
  • a conductive metal foil aluminum or an aluminum alloy is preferable.
  • the positive electrode mixture may contain an ion conductive compound, a thickener, a dispersant, a lubricant, and the like as necessary.
  • the ion conductive compound include polysaccharides such as chitin and chitosan, or a cross-linked product of the polysaccharide.
  • the thickener include carboxymethyl cellulose and polyvinyl alcohol.
  • the positive electrode can be formed, for example, by applying a paste-like positive electrode mixture to a positive electrode current collector, drying, and pressure forming, or by pressing a powdery positive electrode mixture on the positive electrode current collector. can get.
  • the thickness of the positive electrode is usually 0.04 mm or more and 0.15 mm or less.
  • a positive electrode having an arbitrary electrode density can be obtained by adjusting the pressure applied during molding.
  • the pressure applied during the molding is 1t / cm 2 ⁇ 3t / cm 2 is preferably about.
  • the negative electrode is a sheet-like electrode composed of a negative electrode active material, a binder, and a negative electrode mixture containing a conductive additive added as necessary, and a negative electrode current collector bonded to the negative electrode mixture. Can be used. Further, as the negative electrode, a pellet-type or sheet-shaped negative electrode obtained by forming the above-described negative electrode mixture into a disk shape can also be used.
  • negative electrode active material conventionally known negative electrode active materials can be used.
  • carbon materials such as artificial graphite and natural graphite, metals such as Sn and Si, or metalloid materials can be used.
  • the binder the same binder as that used in the positive electrode can be used.
  • the conductive additive may be added as necessary, or may not be added.
  • conductive carbon powders such as furnace black, ketjen black, and acetylene black; carbon nanotubes, carbon nanofibers, vapor grown carbon fibers, and the like can be used.
  • vapor grown carbon fiber is particularly preferable.
  • the vapor grown carbon fiber preferably has a fiber diameter of 5 nm to 0.2 ⁇ m.
  • the ratio of fiber length / fiber diameter is preferably 5 to 1000.
  • the content of vapor grown carbon fiber is preferably 0.1 to 10% by mass with respect to the dry mass of the negative electrode mixture.
  • examples of the negative electrode current collector include a conductive metal foil, a conductive metal net, and a conductive metal punching metal.
  • a conductive metal foil copper or a copper alloy is preferable.
  • the negative electrode can be formed by, for example, applying a paste-like negative electrode mixture to a negative current collector, drying, and pressure molding, or by pressure molding a granular negative electrode mixture on the negative electrode current collector. can get.
  • the thickness of the negative electrode is usually 0.04 mm or more and 0.15 mm or less.
  • a negative electrode having an arbitrary electrode density can be obtained by adjusting the pressure applied during molding.
  • the pressure applied during the molding is 1t / cm 2 ⁇ 3t / cm 2 is preferably about.
  • non-aqueous electrolyte examples include a non-aqueous electrolyte in which a lithium salt is dissolved in an aprotic solvent.
  • the aprotic solvent is preferably at least one or a mixed solvent selected from the group consisting of ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, and vinylene carbonate.
  • the lithium salt include LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , CH 3 SO 3 Li, and CF 3 SO 3 Li.
  • a so-called solid electrolyte or gel electrolyte can also be used as the nonaqueous electrolyte.
  • the solid electrolyte or gel electrolyte include a polymer electrolyte such as a sulfonated styrene-olefin copolymer, a polymer electrolyte using polyethylene oxide and MgClO 4 , and a polymer electrolyte having a trimethylene oxide structure.
  • the non-aqueous solvent used for the polymer electrolyte is preferably at least one selected from the group consisting of ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, and vinylene carbonate.
  • the lithium secondary battery according to the present embodiment is not limited to the positive electrode, the negative electrode, and the nonaqueous electrolyte, and may include other members as necessary.
  • the lithium secondary battery includes a separator that separates the positive electrode and the negative electrode. May be.
  • the separator is essential when the non-aqueous electrolyte is not a polymer electrolyte, and examples thereof include nonwoven fabrics, woven fabrics, microporous films, and combinations thereof. More specifically, the separator is porous. A polypropylene film, a porous polyethylene film, etc. can be used suitably.
  • the lithium secondary battery according to the present embodiment can be used in various fields.
  • Examples include power generation systems such as power generation systems, wind power generation systems, tidal power generation systems, geothermal power generation systems, heat differential power generation systems, and vibration power generation systems.
  • Example 1 Hydrothermal synthesis After dissolving 123 g of LiOH.H 2 O (Kanto Chemical Co., Ltd. deer special grade) in 700 mL of water in a nitrogen atmosphere glove box in which the oxygen concentration was controlled to 0.5% or less, Stir. Further, 113 g of 85% H 3 PO 4 (special grade 85.0% aqueous solution manufactured by Kanto Chemical Co., Inc.) was gradually added and stirred. This is called A liquid. Next, in a glove box, 1.82 g of ascorbic acid was dissolved in 700 mL of water, and then 272 g of FeSO 4 ⁇ 7H 2 O (special grade manufactured by Kanto Chemical Co., Ltd.) was dissolved. This is called B liquid.
  • LiOH.H 2 O Korean Chemical Co., Ltd. deer special grade
  • liquid A and liquid B were mixed and stirred in a glove box, and then placed in an autoclave and sealed.
  • the autoclave was heated from room temperature to 200 ° C. over 1 hour and then heated at 200 ° C. for 3 hours to synthesize LiFePO 4 powder. Then it was naturally cooled.
  • (2) Washing Next after the autoclave is cooled to room temperature, the produced LiFePO 4 is taken out, and Li 2 SO 4 is dissolved in a ratio of 5.498 g to 100 g of ion-exchanged water (Li concentration 1 mol / L). And filtered for 3 minutes.
  • the kneaded mixture was applied to an Al foil at a thickness of 30 ⁇ m, dried at 90 ° C., and then pressed so that the density of the positive electrode material was 2.2 g / cm 3 to obtain a positive electrode plate.
  • (6) Preparation of negative electrode plate 95 g of mesocarbon microbead graphite (manufactured by Osaka Gas Co., Ltd.) as a negative electrode material, 5 g of acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive auxiliary agent, and PVDF (as a binder) 5 g of Kureha Chemical Co., Ltd.) and 50 g of NMP (Kishida Chemical Co., Ltd.) as a solvent were added and kneaded until uniform.
  • mesocarbon microbead graphite manufactured by Osaka Gas Co., Ltd.
  • 5 g of acetylene black manufactured by Denki Kagaku
  • the kneaded mixture was applied to a Cu foil with a thickness of 35 ⁇ m, dried at 90 ° C., and then pressed so that the density of the negative electrode material was 1.5 g / cm 3 to obtain a negative electrode plate.
  • a microporous film made of polypropylene (Celgard 2400 (manufactured by Hoechst Celanese)) and a negative electrode plate are stacked as a separator on the prototyped positive electrode plate, and EC ( A solution obtained by dissolving 1.0 mol / L of LiPF 6 in a mixed solution of ethylene carbonate) and EMC (ethyl methyl carbonate) was put in a coin battery.
  • Example 2 an evaluation battery was produced under the same conditions as in Example 1 except for the cleaning step.
  • the details of the specific cleaning process and the results of the charge / discharge test are as follows. (1) Washing After the autoclave was cooled to room temperature, the produced LiFePO 4 was taken out, and a solution (Li concentration 0.1 mol / L) in which Li 2 CO 3 was dissolved in a ratio of 0.370 g to 100 g of ion-exchanged water. Filtered and washed for 3 minutes. (2) Charge / Discharge Test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Example 3 An evaluation battery was produced under the same conditions as in Example 1 except for the cleaning step.
  • the details of the specific cleaning process and the results of the charge / discharge test are as follows. (1) Washing After the autoclave was cooled to room temperature, the produced LiFePO 4 was taken out, and a solution (Li concentration 0.01 mol / L) in which Li 3 PO 4 was dissolved at a ratio of 0.0386 g to 100 g of ion-exchanged water. Filtered and washed for 3 minutes. (2) Charge / Discharge Test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Example 4 an evaluation battery was produced under the same conditions as in Example 1 except for the cleaning step.
  • the details of the specific cleaning process and the results of the charge / discharge test are as follows. (1) Washing After the autoclave was cooled to room temperature, the produced LiFePO 4 was taken out, and a solution (Li concentration 0.001 mol / L) in which Li 3 PO 4 was dissolved at a ratio of 0.00386 g to 100 g of ion-exchanged water. Filtered and washed for 3 minutes. (2) Charge / Discharge Test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • the discharge capacities at 0.1 C, 0.2 C, 0.5 C, 1 C, and 2 C are 146.4 mAh / g, 144.4 mAh / g, 140.8 mAh / g, 133.9 mAh / g, and 124.4 mAh / g, respectively. there were.
  • the evaluation results are shown in Table 2.
  • Comparative Example 1 An evaluation battery was produced under the same conditions as in Example 1 except for the cleaning step.
  • the details of the specific cleaning process and the results of the charge / discharge test are as follows. (1) Washing After the autoclave was cooled to room temperature, the produced LiFePO 4 was taken out, filtered and washed with ion-exchanged water for 3 minutes. (2) Charging / discharging test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Comparative Example 2 In Comparative Example 2, an evaluation battery was produced under the same conditions as in Example 1 except for the carbon coating step.
  • the specific contents of the carbon coating process and the results of the charge / discharge test are as follows. (1) Carbon coating The dried LiFePO 4 powder is heated from room temperature to 700 ° C. in 90 minutes in a mixed gas of 98.8% nitrogen and 1.2% oxygen, heated for 5 hours, and then naturally cooled. Is different from Example 1 in that the periphery of the LiFePO 4 particles is covered with carbon. (2) Charging / discharging test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Comparative Example 3 In Comparative Example 3, an evaluation battery was produced under the same conditions as in Example 1 except for the carbon coating step.
  • the specific contents of the carbon coating process and the results of the charge / discharge test are as follows. (1) Carbon coating The temperature of the dried LiFePO 4 powder was raised from room temperature to 350 ° C. in nitrogen in 90 minutes, then heated for 5 hours, and then naturally cooled, so that carbon was coated around the LiFePO 4 particles. Is different from the first embodiment. (2) Charging / discharging test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Comparative Example 4 An evaluation battery was produced under the same conditions as in Example 1 except for the carbon coating step.
  • the specific contents of the carbon coating process and the results of the charge / discharge test are as follows. (1) Carbon coating The temperature of the dried LiFePO 4 powder was raised from room temperature to 950 ° C. in 90 minutes in 90 minutes, then heated for 5 hours, and then naturally cooled to coat carbon around the LiFePO 4 particles. Is different from the first embodiment. (2) Charging / discharging test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.
  • Comparative Example 5 An evaluation battery was produced under the same conditions as in Example 1 except for the carbon coating step.
  • the specific contents of the carbon coating process and the results of the charge / discharge test are as follows. (1) Carbon coating The dried LiFePO 4 powder was heated in nitrogen from room temperature to 700 ° C. in 90 minutes, then heated for 0.5 hours, and then naturally cooled to coat carbon around the LiFePO 4 particles. This is different from the first embodiment. (2) Charging / discharging test As in Example 1, after charging at a constant current and a constant voltage up to 3.9 V at a temperature of 25 ° C.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de production d'un matériau actif d'électrode positive pour une batterie secondaire au lithium, grâce auquel il est possible de configurer une batterie secondaire au lithium dans laquelle la capacité de décharge est améliorée et l'élution d'ions de lithium à partir d'un phosphate métallique de lithium est supprimée lors du lavage du phosphate métallique de lithium après sa synthétisation. Ce procédé de production d'un matériau actif d'électrode positive pour une batterie secondaire au lithium est caractérisé par la synthétisation d'un phosphate métallique de lithium représenté par la formule de composition LiMPO4 (l'élément M représentant un ou plusieurs métaux de transition sélectionnés parmi Fe, Mn, Co et Ni) et par le lavage dudit phosphate métallique de lithium en utilisant un liquide de nettoyage qui contient des ions de lithium.
PCT/JP2012/061036 2011-04-28 2012-04-25 Procédé de production de matériau actif d'électrode positive pour batterie secondaire au lithium WO2012147767A1 (fr)

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US14/113,731 US9745194B2 (en) 2011-04-28 2012-04-25 Method of producing cathode active material for lithium secondary battery
CN201280020124.5A CN103503207B (zh) 2011-04-28 2012-04-25 锂二次电池用正极活性物质的制造方法
JP2013512393A JP6055761B2 (ja) 2011-04-28 2012-04-25 リチウム二次電池用正極活物質の製造方法

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US11251430B2 (en) 2018-03-05 2022-02-15 The Research Foundation For The State University Of New York ϵ-VOPO4 cathode for lithium ion batteries
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JP2017045632A (ja) * 2015-08-27 2017-03-02 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池
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KR20210111735A (ko) * 2016-01-13 2021-09-13 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질의 제조 방법
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JP2020115484A (ja) * 2020-04-28 2020-07-30 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質、および非水系電解質二次電池
WO2023096201A1 (fr) * 2021-11-24 2023-06-01 주식회사 엘지에너지솔루션 Méthode de préparation de matériau actif d'électrode positive pour batterie secondaire au lithium et matériau actif d'électrode positive ainsi préparé

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